CN111151248A - Method for catalyzing heterocyclic halogen-containing organic matter hydrogenation dehalogenation by using supported metal oxide - Google Patents

Method for catalyzing heterocyclic halogen-containing organic matter hydrogenation dehalogenation by using supported metal oxide Download PDF

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CN111151248A
CN111151248A CN201910531574.4A CN201910531574A CN111151248A CN 111151248 A CN111151248 A CN 111151248A CN 201910531574 A CN201910531574 A CN 201910531574A CN 111151248 A CN111151248 A CN 111151248A
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mixture
chloro
cyanopyridine
mass
mass percent
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王亮
肖丰收
王海
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract

The invention relates to a catalyst for hydrogenation and dehalogenation, and aims to provide a method for catalyzing heterocycle halogen-containing organic matters to be hydrogenated and dehalogenated by using supported metal oxides. The method comprises the following steps: uniformly mixing a solvent, heterocyclic halogen-containing organic matters, a neutralizer and a catalyst material; filling hydrogen into the reaction container until the pressure is 0.1-3.0 MPa; controlling the reaction temperature to be 25-180 ℃ and the reaction time to be 0.1-24 h; and catalyzing and dehalogenating in the reaction process to finally obtain the dehalogenated heterocyclic compound. The method can effectively regulate and control the selectivity of products in the process of dehalogenation of heterocyclic halogen-containing organic matters, and effectively regulate and control the adsorption of organic molecules such as pyridine, thiophene and the like on the surface of a catalytic material by regulating and controlling the chemical coordination environment of metal components, thereby efficiently preparing important compounds in the chemical and agricultural processes. The catalytic material is stable and recyclable in the dehalogenation process, no toxic and harmful byproducts are generated in the whole reaction process, and the catalyst is green and environment-friendly and has high industrial application prospect.

Description

Method for catalyzing heterocyclic halogen-containing organic matter hydrogenation dehalogenation by using supported metal oxide
Technical Field
The invention relates to a catalyst for catalyzing heterocyclic halogen-containing organic matter hydrogenation and dehalogenation, in particular to a method for catalyzing heterocyclic halogen-containing organic matter hydrogenation and dehalogenation by using a supported metal oxide material.
Background
In recent years, with the rapid development of chemical and chemical industries, organic heteroatom compounds have been widely and importantly used in the fields of agricultural chemicals, medicines, organic synthesis, and chemical industry. Meanwhile, the great emission of the heteroatom organic matters containing halogen atoms in the industrial production process is also paid attention by governments and researchers of various countries, mainly because most of the chlorine-containing organic matters have the characteristics of environmental durability, biological accumulation, high toxicity and the like due to the halogen atoms contained in the structures, are not easy to decompose or biodegrade, so that the substances are continuously accumulated in the nature, the damage to the environment is increasingly serious, and the harm to the health of human bodies is increasingly prominent. Such as serious pollution of water and soil caused by organochlorine pesticide. Therefore, if the halogen in the heteroatom organic matter containing halogen atoms can be effectively removed, the harm of the compound to the environment and the living beings can be reduced, and simultaneously the organic heteroatom compound with high added value can be obtained. The heterocyclic halogen-containing organic matter is dehalogenated most directly at present, the method with the most prospect is hydrogenation dehalogenation, the heterocyclic organic matter containing halogen can be selectively converted into the dehalogenated high-value-added organic heteroatom compound under the action of the catalyst under a relatively mild condition and then applied to the chemical production process, and the used heterogeneous catalyst can be recycled, so that the catalyst cost can be effectively reduced, and therefore, the method is the most economic and green method for dehalogenating the heterocyclic halogen-containing organic matter and is the most promising method.
The most key in the process of hydrodehalogenation of heterocyclic halogen-containing organic matters is to select a hydrodehalogenation catalytic material with high activity, high selectivity and high stability. Since the 80 s of the last century, people have increasingly widely researched hydrodehalogenation catalysts, but catalytic materials with real industrial application prospects are few, and mainly most of the hydrodehalogenation catalysts have the common reasons of poor reaction activity, poor target product selectivity, unstable catalytic material structures and the like. For example, when some halogen-containing organic substances containing two or more groups capable of being hydrogenated are subjected to hydrodehalogenation, functional groups other than halogen are easily hydrogenated, so that the problem of low product selectivity is caused; in addition, especially for the hydrodehalogenation reaction system containing nitrogen and sulfur compounds, the substrates in the category are easy to cause the loss and sintering of the active components of the catalytic material, so that the regeneration and recovery of the catalyst after use are difficult, and the industrial scale-up production is difficult. Therefore, research and development of a catalytic material which can be used for catalyzing heterocyclic halogen-containing organic matters to be subjected to hydrogenation and dehalogenation and has high efficiency, high selectivity and high stability have important significance.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a method for catalyzing heterocyclic halogen-containing organic matters to be hydrodehalogenated by using supported metal oxides.
In order to solve the technical problem, the solution of the invention is as follows:
the method for catalyzing heterocyclic halogen-containing organic matters to be hydrodehalogenated by using supported metal oxides comprises the following steps:
(1) adding a solvent, heterocyclic halogen-containing organic matters, a neutralizer and a catalyst material into a sealable reaction vessel, and uniformly mixing; in the mixture, the mass percent of the catalyst material is 0.01-10%, the mass percent of the heterocyclic halogen-containing organic matter is 0.01-76.4%, the mass percent of the neutralizing agent is 0.01-19.6%, and the balance is solvent;
(2) filling hydrogen into the reaction container until the pressure is 0.1-3.0 MPa; controlling the reaction temperature to be 25-180 ℃ and the reaction time to be 0.1-24 hours; catalyzing and dehalogenating in the reaction process to finally obtain a dehalogenated heterocyclic compound;
in the catalyst material, the carrier is cerium oxide (CeO)2) Titanium oxide (TiO)2) Iron oxide (Fe)2O3Or Fe3O4) Manganese oxide (MnO)2、Mn3O4、Mn2O3Or MnO), cobalt oxide (Co)3O4) Alumina (Al)2O3) Silicon oxide (SiO)2) One or more of magnesium oxide (MgO) and activated carbon; the metal component loaded by the carrier is one or more of Au, Pd, Pt, Rh, Ir, Ni and Sn, and the mass percent of the metal component in the whole catalyst material is 0.1-30%.
In the present invention, the solvent is any one or more of the following: water, methanol, ethanol, tert-butanol, tert-amyl alcohol, toluene, dichloromethane, chloroform, dimethyl sulfoxide or acetone.
In the invention, the heterocyclic halogen-containing organic matter is any one or more of the following: 2-chloropyridine, 2-bromopyridine, 2-iodopyridine, 2-chlorothiophene, 2-chlorofuran, 2, 3-dichloropyridine, 2, 3-dibromopyridine, 2, 5-dichlorothiophene, 2-chloro-6-methoxypyridine, 2-chloro-6-trifluoromethylpyridine, 2-chloro-6-cyanopyridine, 5-chloro-3-thiophenecarbonitrile, 2-methyl-6-chloropyridine, 2-chloro-6-vinylpyridine, methyl 6-chloro-2-pyridinecarboxylate, 2, 6-dichloro-4- (trifluoromethyl) pyridine, 2, 6-dichloro-4-methoxypyridine, 2, 6-dichloro-4-cyanopyridine, 2, 3-dichlorothiophene, 2, 5-dichlorothiophene-carbonitrile, 2-chloro-6-methoxypyridine, 2-chloro-6-trifluoromethylpyridine, 2-chloro-, 3-cyano-2, 6-dichloro-4- (trifluoromethyl) pyridine, 3-methoxy-2, 6-dichloro-4- (trifluoromethyl) pyridine, 3-carboxylic acid methyl ester-2, 6-dichloro-4- (trifluoromethyl) pyridine, 3-cyano-2, 6-dichloro-4- (methoxy) pyridine.
In the present invention, the neutralizing agent is any one of the following: pyridine, triethylamine, diethylamine, sodium bicarbonate or sodium carbonate (a reagent capable of neutralising with an acid).
Description of the inventive principles:
the invention takes Au, Pd, Pt, Rh, Ir, Ni, Sn and other metals as the metal active components loaded in the catalytic material, and can utilize the excellent capability of activating and dissociating hydrogen of the metals to oxidize cerium (CeO)2) Titanium oxide (TiO)2) Iron oxide (Fe)2O3Or Fe3O4) Manganese oxide (MnO)2、Mn3O4、Mn2O3Or MnO), cobalt oxide (Co)3O4) Alumina (Al)2O3) Silicon oxide (SiO)2) The catalyst comprises a catalyst carrier, magnesium oxide (MgO), activated carbon and the like, can uniformly disperse loaded metal active components, modifies the metal components by utilizing metal-carrier interaction, regulates and controls adsorption of reactant molecules so as to regulate and control reaction selectivity, and stabilizes the metal components so as to ensure high stability, thereby efficiently catalyzing dehalogenation of aromatic halogen-containing organic matters. No toxic and harmful by-products are generated in the whole reaction process,is green and environment-friendly.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention relates to a method for efficiently preparing important compounds in chemical and agricultural processes by effectively regulating and controlling the selectivity of products in the dehalogenation process of heterocyclic halogen-containing organic matters through regulating and controlling metal components loaded by catalytic materials and a catalytic material carrier, enabling high-selectivity dehalogenation to be still realized even when the halogen-containing organic matters contain two or more than two reducible functional groups, and effectively regulating and controlling the adsorption of organic molecules such as pyridine, thiophene and the like on the surface of the catalytic materials through regulating and controlling the chemical coordination environment of the metal components.
2. The invention provides a method for more catalyzing the dehalogenation of heterocyclic halogen-containing organic matters, and the catalytic material is stable and recyclable in the dehalogenation process, no toxic and harmful by-products are generated in the whole reaction process, so that the method is green and environment-friendly and has high industrial application prospect.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments. The reactions of the following examples were all carried out in a closable reaction vessel. The examples may provide those skilled in the art with a more complete understanding of the present invention, and are not intended to limit the invention in any way.
Example 1
100mg of Au/CeO was added to 6g of ethanol2(Au load mass percent: 5%, whole catalytic material in the mixture mass percent: 1.7%), 60mg 2-chloro-6-cyanopyridine (in the mixture mass percent: 1.0%), 60mg diethylamine (in the mixture mass percent: 1.0%), adding 0.5MPa hydrogen, mixing well; the reaction was carried out at 80 ℃ for 5 hours, with a conversion of 74.9% for 2-chloro-6-cyanopyridine and a selectivity of 85.1% for the corresponding 2-cyanopyridine.
Example 2
100mg of Pd/CeO was added to 6g of ethanol2(Pd support mass% 5%, mass% of the entire catalytic material in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture: 1.0%), 60mg of diethylamine (in the mixture: 1.0%)The mass percentage of the composition is as follows: 1.0 percent) and 0.5MPa of hydrogen are added and mixed evenly; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity for the corresponding 2-cyanopyridine of>99.0％。
Example 3
100mg of Pt/CeO was added to 6g of ethanol2(Pt loading mass% 5%, the mass% of the whole catalytic material in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture: 1.0%), 60mg of diethylamine (mass% in the mixture: 1.0%), hydrogen gas of 0.5MPa was charged and mixed uniformly; the reaction is carried out for 5 hours at the temperature of 80 ℃, the conversion rate of the 2-chloro-6-cyanopyridine is 98.4 percent, and the selectivity of the corresponding 2-cyanopyridine is>99.0％。
Example 4
100mg of Rh/CeO was added to 6g of ethanol2(Rh loading mass percent: 5%, mass percent of the whole catalytic material in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa was charged, and the mixture was mixed uniformly; the reaction was carried out at 80 ℃ for 5 hours, with a conversion of 69.0% for 2-chloro-6-cyanopyridine and a selectivity for the corresponding 2-cyanopyridine of 90.1%.
Example 5
100mg Ir/CeO was added to 6g ethanol2(Ir load mass% 5%, the whole catalytic material mass% in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture: 1.0%), 60mg of diethylamine (mass% in the mixture: 1.0%), hydrogen gas of 0.5MPa was charged and mixed uniformly; the reaction was carried out at 80 ℃ for 5 hours, and the conversion of 2-chloro-6-cyanopyridine was 58.8%, which corresponds to a selectivity of 73.5% for 2-cyanopyridine.
Example 6
100mg of Ni/CeO was added to 6g of ethanol2(Ni-supporting mass% 5%, mass% of the entire catalytic material in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture: 1.0%), 60mg of diethylamine (mass% in the mixture: 1.0%), and a water-soluble catalyst in the mixtureHydrogen of 0.5MPa, and mixing uniformly; the reaction was carried out at 80 ℃ for 5 hours, and the conversion of 2-chloro-6-cyanopyridine was 70.4%, which corresponds to a selectivity for 2-cyanopyridine of 97.9%.
Example 7
100mg of Sn/CeO is added into 6g of ethanol2(Sn loading mass percent: 5%, mass percent of the whole catalytic material in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), charging 0.5MPa of hydrogen, and mixing uniformly; the reaction was carried out at 80 ℃ for 5 hours, with a conversion of 2-chloro-6-cyanopyridine of 32.6% and a selectivity of the corresponding 2-cyanopyridine of 50.5%.
Example 8
100mg of Pd-Sn/CeO is added into 6g of ethanol2(Pd loading mass% 2.5%, Sn loading mass% 2.5%, the mass% of the whole catalytic material in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture: 1.0%), 60mg of diethylamine (mass% in the mixture: 1.0%), hydrogen gas of 0.5MPa was flushed and mixed uniformly; the reaction is carried out for 5 hours at the temperature of 80 ℃, the conversion rate of the 2-chloro-6-cyanopyridine is 96.0 percent, and the selectivity of the corresponding 2-cyanopyridine is>99.0％。
Example 9
Adding 100mg Pd-Ni/CeO into 6g ethanol2(Pd loading mass% 2.5%, Ni loading mass% 2.5%, the mass% of the whole catalytic material in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture: 1.0%), 60mg of diethylamine (mass% in the mixture: 1.0%), hydrogen gas of 0.5MPa was flushed and mixed uniformly; the reaction is carried out for 5 hours at the temperature of 80 ℃, the conversion rate of the 2-chloro-6-cyanopyridine is 98.2 percent, and the selectivity of the corresponding 2-cyanopyridine is>99.0％。
Based on the fact that the metal palladium (Pd) shows the optimal catalytic performance in each metal component, the metal palladium (Pd) is selected as the supported metal component, and the influence of the metal palladium (Pd) supported by other carriers on the hydrogenation and dehalogenation of the heterocyclic halogen-containing organic matter is continuously examined.
Example 10
100mg Pd/TiO in 6g ethanol2(Pd loading mass% is 5%, the mass% of the whole catalytic material in the mixture is 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture is 1.0%), 60mg of diethylamine (mass% in the mixture is 1.0%), hydrogen gas of 0.5MPa is added, and the mixture is uniformly mixed; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity of 94.9% for the corresponding 2-cyanopyridine.
Example 11
100mg Pd/Fe was added to 6g ethanol2O3(Pd loading mass% is 5%, the mass% of the whole catalytic material in the mixture is 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture is 1.0%), 60mg of diethylamine (mass% in the mixture is 1.0%), hydrogen gas of 0.5MPa is added, and the mixture is uniformly mixed; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity of 93.7% for the corresponding 2-cyanopyridine.
Example 12
100mg Pd/Fe was added to 6g ethanol3O4(Pd loading mass% is 5%, the mass% of the whole catalytic material in the mixture is 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture is 1.0%), 60mg of diethylamine (mass% in the mixture is 1.0%), hydrogen gas of 0.5MPa is added, and the mixture is uniformly mixed; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity to the corresponding 2-cyanopyridine of 85.0%.
Example 13
Adding 100mg Pd/MnO into 6g ethanol2(Pd loading mass% is 5%, the mass% of the whole catalytic material in the mixture is 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture is 1.0%), 60mg of diethylamine (mass% in the mixture is 1.0%), hydrogen gas of 0.5MPa is added, and the mixture is uniformly mixed; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity of 49.2% for the corresponding 2-cyanopyridine.
Example 14
100mg Pd/Mn was added to 6g ethanol3O4(Pd loading mass% is 5%, the mass% of the whole catalytic material in the mixture is 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture is 1.0%), 60mg of diethylamine (mass% in the mixture is 1.0%), hydrogen gas of 0.5MPa is added, and the mixture is uniformly mixed; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity of 56.4% for the corresponding 2-cyanopyridine.
Example 15
100mg Pd/Mn was added to 6g ethanol2O3(Pd loading mass% is 5%, the mass% of the whole catalytic material in the mixture is 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture is 1.0%), 60mg of diethylamine (mass% in the mixture is 1.0%), hydrogen gas of 0.5MPa is added, and the mixture is uniformly mixed; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity of 20.3% for the corresponding 2-cyanopyridine
Example 16
100mg of Pd/MnO (Pd loading mass% 5%, mass% of the whole catalyst material in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture: 1.0%) and 60mg of diethylamine (mass% in the mixture: 1.0%) were added to 6g of ethanol, and hydrogen gas of 0.5MPa was flushed thereinto and mixed uniformly; the reaction is carried out for 5 hours at the temperature of 80 ℃, the conversion rate of the 2-chloro-6-cyanopyridine is more than 99.0 percent, and the selectivity of the corresponding 2-cyanopyridine is 49.9 percent
Example 17
100mg Pd/Co was added to 6g ethanol3O4(Pd loading mass% is 5%, the mass% of the whole catalytic material in the mixture is 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture is 1.0%), 60mg of diethylamine (mass% in the mixture is 1.0%), hydrogen gas of 0.5MPa is added, and the mixture is uniformly mixed; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity of 36.3% for the corresponding 2-cyanopyridine
Example 18
Adding into 6g of ethanol100mg Pd/Al2O3(Pd loading mass% is 5%, the mass% of the whole catalytic material in the mixture is 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture is 1.0%), 60mg of diethylamine (mass% in the mixture is 1.0%), hydrogen gas of 0.5MPa is added, and the mixture is uniformly mixed; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% and corresponding 2-cyanopyridine selectivity 77.8%
Example 19
100mg of Pd/SiO are added to 6g of ethanol2(Pd loading mass% is 5%, the mass% of the whole catalytic material in the mixture is 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture is 1.0%), 60mg of diethylamine (mass% in the mixture is 1.0%), hydrogen gas of 0.5MPa is added, and the mixture is uniformly mixed; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity of 68.5% for the corresponding 2-cyanopyridine
Example 20
100mg of Pd/MgO (Pd loading mass percentage: 5%, mass percentage of the whole catalytic material in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percentage in the mixture: 1.0%), 60mg of diethylamine (mass percentage in the mixture: 1.0%) were added to 6g of ethanol, and hydrogen gas of 0.5MPa was added to the mixture to mix the mixture uniformly; the reaction is carried out for 5 hours at the temperature of 80 ℃, the conversion rate of the 2-chloro-6-cyanopyridine is more than 99.0 percent, and the selectivity of the corresponding 2-cyanopyridine is 49.2 percent
Example 21
100mg of Pd/C (Pd loading mass% is 5%, mass% of the whole catalytic material in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture: 1.0%), 60mg of diethylamine (mass% in the mixture: 1.0%) were added to 6g of ethanol, and hydrogen gas of 0.5MPa was added thereto and mixed uniformly; the reaction is carried out for 5 hours at the temperature of 80 ℃, the conversion rate of the 2-chloro-6-cyanopyridine is more than 99.0 percent, and the selectivity of the corresponding 2-cyanopyridine is 11.3 percent
Based on the fact that the cerium oxide supported metal palladium (Pd) shows the optimal catalytic performance in each studied metal component, the influence of the change of other parameters or conditions on the catalytic hydrogenation and dehalogenation of the heterocyclic halogen-containing organic compound is continuously studied for the catalytic material.
Example 22
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass% 0.1%, the whole catalytic material mass% in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture: 1.0%), 60mg of diethylamine (mass% in the mixture: 1.0%), hydrogen gas of 0.5MPa was added and mixed uniformly; the reaction is carried out for 5 hours at the temperature of 80 ℃, the conversion rate of the 2-chloro-6-cyanopyridine is 63.2 percent, and the selectivity of the corresponding 2-cyanopyridine is>99.0％。
Example 23
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 15.0%, mass percent of the whole catalytic material in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), charging 0.5MPa of hydrogen, and mixing uniformly; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity of 43.6% for the corresponding 2-cyanopyridine
Example 24
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 30.0%, mass percent of the whole catalytic material in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), charging 0.5MPa of hydrogen, and mixing uniformly; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a corresponding selectivity to 2-cyanopyridine of 8.9%.
Example 25
Adding 1mg Pd/CeO into 6g ethanol2(Pd loading mass percent: 5%, mass percent of the whole catalytic material in the mixture: 0.01%), 60mg of 2-chloro-6-cyanopyridine (mass percent in the mixture: 0.98%), 60mg of diethylamine (mass percent in the mixture: 0.98%), charging 0.5MPa of hydrogen, and mixing uniformly; the reaction is carried out for 5 hours at the temperature of 80 ℃,the conversion of 2-chloro-6-cyanopyridine was 6.3% with a corresponding selectivity to 2-cyanopyridine of 38.2%.
Example 26
Adding 300mg Pd/CeO into 6g ethanol2(Pd loading mass% is 5%, the mass% of the whole catalytic material in the mixture is 4.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture is 0.93%), 60mg of diethylamine (mass% in the mixture is 0.93%), hydrogen gas of 0.5MPa is added, and the mixture is uniformly mixed; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity of 74.9% for the corresponding 2-cyanopyridine.
Example 27
700mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass% is 5%, the mass% of the whole catalytic material in the mixture is 10.0%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture is 0.87%), 60mg of diethylamine (mass% in the mixture is 0.87%), hydrogen gas of 0.5MPa is added, and the mixture is uniformly mixed; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a corresponding selectivity to 2-cyanopyridine of 35.5%.
The Pd/CeO with the Pd loading of 5 percent is continuously adopted because the loading of the metal Pd is too low or the catalyst feeding is too little to cause the insufficient activity of the catalytic material and the loading is too high or the catalyst feeding is too much to cause the low selectivity of the product2The catalytic material and the catalyst charge amount are 100mg for research.
Example 28
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa was added and mixed uniformly; the reaction was carried out at 80 ℃ for 0.1 hour, with a conversion of 4.9% for 2-chloro-6-cyanopyridine and a selectivity for the corresponding 2-cyanopyridine of 66.8%.
Example 29
100mg of Pd/CeO was added to 6g of ethanol2(Pd supporting MassThe percentage is 5.0 percent, and the mass percentage of the whole catalytic material in the mixture is as follows: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percentage in the mixture: 1.0%), 60mg diethylamine (mass percentage in the mixture: 1.0 percent) and 0.5MPa of hydrogen are added and mixed evenly; the reaction is carried out at 80 ℃ for 0.5 hour, the conversion rate of the 2-chloro-6-cyanopyridine is 20.4 percent, and the selectivity of the corresponding 2-cyanopyridine is>99.0％。
Example 30
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa was added and mixed uniformly; reaction at 80 deg.c for 24 hr and 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity for the corresponding 2-cyanopyridine of<0.1％。
Example 31
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa was added and mixed uniformly; the reaction is carried out for 5 hours at 25 ℃, the conversion rate of the 2-chloro-6-cyanopyridine is 13.6 percent, and the selectivity of the corresponding 2-cyanopyridine is>99.0％。
Example 32
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa was added and mixed uniformly; reaction at 130 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity of 64.0% for the corresponding 2-cyanopyridine.
Example 33
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%; monolith)The mass percentage of each catalytic material in the mixture is as follows: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percentage in the mixture: 1.0%), 60mg diethylamine (mass percentage in the mixture: 1.0 percent) and 0.5MPa of hydrogen are added and mixed evenly; reaction at 180 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity of 28.1% for the corresponding 2-cyanopyridine.
Example 34
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 3.0MPa was charged and mixed uniformly; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a corresponding selectivity to 2-cyanopyridine of 6.6%.
Example 35
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.1MPa was added and mixed uniformly; the reaction is carried out for 5 hours at the temperature of 80 ℃, the conversion rate of the 2-chloro-6-cyanopyridine is 20.3 percent, and the selectivity of the corresponding 2-cyanopyridine is>99.0％。
Example 36
100mg of Pd/CeO was added to 6g of water2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa was added and mixed uniformly; the reaction was carried out at 80 ℃ for 5 hours, with a conversion of 6.2% for 2-chloro-6-cyanopyridine and a selectivity for the corresponding 2-cyanopyridine of 48.1%.
Example 37
100mg of Pd/CeO was added to 6g of methanol2(Pd loading mass% 5.0%; mass of the entire catalytic material in the mixture)The weight percentage is as follows: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percentage in the mixture: 1.0%), 60mg diethylamine (mass percentage in the mixture: 1.0 percent) and 0.5MPa of hydrogen are added and mixed evenly; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity of 46.8% for the corresponding 2-cyanopyridine.
Example 38
100mg of Pd/CeO was added to 6g of t-butanol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa was added and mixed uniformly; the reaction was carried out at 80 ℃ for 5 hours, with a conversion of 2-chloro-6-cyanopyridine of 60.6% and a selectivity of the corresponding 2-cyanopyridine of 95.3%.
Example 39
100mg of Pd/CeO in 6g of tert-amyl alcohol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa was added and mixed uniformly; the reaction was carried out at 80 ℃ for 5 hours, and the conversion of 2-chloro-6-cyanopyridine was 73.8%, which corresponds to a selectivity of 98.1% for 2-cyanopyridine.
Example 40
100mg of Pd/CeO was added to 6g of toluene2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa was added and mixed uniformly; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity for the corresponding 2-cyanopyridine of>99.0％。
EXAMPLE 41
100mg of Pd/CeO was added to 6g of methylene chloride2(Pd loading mass percent: 5.0%, mass percent of the whole catalytic material in the mixture: 1.7%) 60mg of 2-chloro-6-cyanopyridine (mass percentage in the mixture: 1.0%), 60mg diethylamine (mass percentage in the mixture: 1.0 percent) and 0.5MPa of hydrogen are added and mixed evenly; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity of 94.1% for the corresponding 2-cyanopyridine.
Example 42
Adding 100mg Pd/CeO into 6g of trichloromethane2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa was added and mixed uniformly; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity of 96.9% for the corresponding 2-cyanopyridine.
Example 43
100mg of Pd/CeO was added to 6g of dimethyl sulfoxide2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa was added and mixed uniformly; the reaction was carried out at 80 ℃ for 5 hours, with a conversion of 84.5% for 2-chloro-6-cyanopyridine and a selectivity of 82.9% for the corresponding 2-cyanopyridine.
Example 44
100mg of Pd/CeO was added to 6g of acetone2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa was added and mixed uniformly; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a corresponding selectivity to 2-cyanopyridine of 90.9%.
Based on that in the screening of the solvent, the catalytic material shows better catalytic performance in ethanol, tertiary butanol, tertiary amyl alcohol, toluene and chloroform, the ethanol is continuously adopted as the solvent for research.
Example 45
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass% is 5%, the mass% of the whole catalytic material in the mixture is 1.6%), 1mg of 2-chloro-6-cyanopyridine (mass% in the mixture is 0.01%), 60mg of diethylamine (mass% in the mixture is 0.97%), hydrogen gas of 0.5MPa is added, and the mixture is uniformly mixed; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity for the corresponding 2-cyanopyridine of<0.1％。
Example 46
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass% is 5%, the mass% of the whole catalytic material in the mixture is 0.98%), 4g of 2-chloro-6-cyanopyridine (mass% in the mixture is 40.0%), 60mg of diethylamine (mass% in the mixture is 0.59%), hydrogen gas of 0.5MPa is added, and the mixture is uniformly mixed; the reaction was carried out at 80 ℃ for 5 hours, with a conversion of 25.5% for 2-chloro-6-cyanopyridine and a selectivity for the corresponding 2-cyanopyridine of 95.2%.
Example 47
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass% is 5%, the mass% of the whole catalytic material in the mixture is 0.38%), 20g of 2-chloro-6-cyanopyridine (mass% in the mixture is 76.4%), 60mg of diethylamine (mass% in the mixture is 0.22%), hydrogen gas of 0.5MPa is added, and the mixture is uniformly mixed; the reaction was carried out at 80 ℃ for 5 hours, with a conversion of 2-chloro-6-cyanopyridine of 10.7% and a selectivity of the corresponding 2-cyanopyridine of 74.5%.
Example 48
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, mass percent of the whole catalytic material in the mixture: 1.7%), 60mg of 2-chloropyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa was added and the mixture was mixed uniformly; reaction at 80 ℃ for 5 hours, 2-chloropyridine conversion>99.0% with a selectivity for pyridine of>99.0％。
Example 49
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, mass percent of the whole catalytic material in the mixture: 1.7%), 60mg of 2-bromopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa was added and the mixture was mixed uniformly; reaction at 80 ℃ for 5 hours, 2-bromopyridine conversion rate>99.0% with a selectivity for pyridine of>99.0％。
Example 50
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, mass percent of the whole catalytic material in the mixture: 1.7%), 60mg of 2-iodopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa was added and the mixture was mixed uniformly; the reaction is carried out for 5 hours at the temperature of 80 ℃, the conversion rate of the 2-iodopyridine is 82.9 percent, and the selectivity of the corresponding pyridine is>99.0％。
Example 51
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 2-chlorothiophene (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa is added, and the mixture is uniformly mixed; reaction at 80 deg.c for 5 hr and 2-chlorothiophene conversion rate>99.0% with a selectivity for the corresponding thiophene of>99.0％。
Example 52
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, mass percent of the whole catalytic material in the mixture: 1.7%), 60mg of 2-chlorofuran (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa was added and the mixture was mixed uniformly; reaction at 80 ℃ for 5 hours, 2-chlorofuran conversion>99.0% with a selectivity for furan of>99.0％。
Example 53
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%; entire catalytic material in mixtureThe mass percentage of (A) is as follows: 1.7%), 60mg of 2, 3-dichloropyridine (mass percentage in the mixture: 1.0%), 60mg diethylamine (mass percentage in the mixture: 1.0 percent) and 0.5MPa of hydrogen are added and mixed evenly; reaction at 80 deg.c for 5 hr and 2, 3-dichloropyridine converting rate>99.0% with a selectivity for pyridine of>99.0％。
Example 54
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 2, 3-dibromopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa is added, and the mixture is uniformly mixed; reaction at 80 ℃ for 5 hours, and conversion rate of 2, 3-dibromopyridine>99.0% with a selectivity for pyridine of>99.0％。
Example 55
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 2, 5-dichlorothiophene (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), charging 0.5MPa of hydrogen, and mixing uniformly; reaction at 80 deg.c for 5 hr and 2, 5-dichlorothiophene converting rate>99.0% with a selectivity for the corresponding thiophene of>99.0％。
Example 56
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 2-chloro-6-methoxypyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), adding 0.5MPa of hydrogen, and mixing uniformly; reaction at 80 ℃ for 5 hours, conversion rate of 2-chloro-6-methoxypyridine>99.0% with a selectivity for the corresponding 2-methoxypyridine of>99.0％。
Example 57
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass% 5.0%, mass% of the entire catalytic material in the mixture: 1.7%), 60mg of 2-chloro-6-trifluoro-2-chloro-6Picoline (mass% in the mixture: 1.0%), 60mg diethylamine (mass% in the mixture: 1.0%), hydrogen gas of 0.5MPa was added, and the mixture was mixed uniformly; reaction at 80 deg.c for 5 hr and 2-chloro-6-trifluoromethylpyridine converting rate>99.0% with a selectivity for the corresponding 2-trifluoromethylpyridine of>99.0％。
Example 58
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa was added and mixed uniformly; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity for the corresponding 2-cyanopyridine of>99.0％。
Example 59
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 5-chloro-3-thiophenecarbonitrile (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa was added, and the mixture was mixed uniformly; reaction at 80 deg.c for 5 hr to obtain 5-chloro-3-thiophenecarbonitrile>99.0% with a selectivity for the corresponding 3-cyanothiophene of>99.0％。
Example 60
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 2-methyl-6-chloropyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa was added and mixed uniformly; reaction at 80 deg.c for 5 hr, 2-methyl-6-chloropyridine conversion rate>99.0% with a selectivity for the corresponding 2-methylpyridine of>99.0％。
Example 61
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, mass percent of the whole catalytic material in the mixture: 1.7%), 60mg of 2-chloro-6-Vinylpyridine (mass% in the mixture: 1.0%), 60mg diethylamine (mass% in the mixture: 1.0%), hydrogen gas of 0.5MPa was added and mixed uniformly; reaction at 80 deg.c for 5 hr, 2-chloro-6-vinylpyridine conversion>99.0% corresponding to a selectivity of 83.9% for 2-vinylpyridine.
Example 62
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of methyl 6-chloro-2-pyridinecarboxylate (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), hydrogen gas of 0.5MPa was added and mixed uniformly; reaction at 80 deg.c for 5 hr to obtain 6-chloro-2-methyl picolinate>99.0% with a selectivity to methyl 2-picolinate of>99.0％。
Example 63
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 2, 6-dichloro-4- (trifluoromethyl) pyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), 0.5MPa of hydrogen gas was added and the mixture was mixed uniformly; reaction at 80 deg.c for 5 hr and conversion rate of 2, 6-dichloro-4- (trifluoromethyl) pyridine>99.0% with a selectivity for the corresponding 4-trifluoromethylpyridine of>99.0％。
Example 64
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, the whole catalytic material in the mixture mass percent: 1.7%), 60mg of 2, 6-dichloro-4-methoxypyridine (in the mixture mass percent: 1.0%), 60mg of diethylamine (in the mixture mass percent: 1.0%), 0.5MPa of hydrogen gas was added and mixed uniformly; reaction at 80 deg.c for 5 hr to obtain 2, 6-dichloro-4-methoxypyridine in high conversion rate>99.0% with a selectivity for the corresponding 4-methoxypyridine of>99.0％。
Example 65
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass% 5.0%; entire catalyst material)The mass percentage of the materials in the mixture is as follows: 1.7%), 60mg of 2, 6-dichloro-4-cyanopyridine (mass percentage in the mixture: 1.0%), 60mg diethylamine (mass percentage in the mixture: 1.0 percent) and 0.5MPa of hydrogen are added and mixed evenly; reaction at 80 deg.c for 5 hr to obtain 2, 6-dichloro-4-cyanopyridine in high conversion rate>99.0% with a selectivity for the corresponding 4-cyanopyridine of>99.0％。
Example 66
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 3-cyano-2, 6-dichloro-4- (trifluoromethyl) pyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), 0.5MPa of hydrogen gas was added, and the mixture was mixed uniformly; the reaction was carried out at 80 ℃ for 5 hours, with a conversion of 83.7% for 3-cyano-2, 6-dichloro-4- (trifluoromethyl) pyridine and a selectivity of 92.5% for the corresponding 3-cyano-4-trifluoromethylpyridine.
Example 67
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 3-methoxy-2, 6-dichloro-4- (trifluoromethyl) pyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), 0.5MPa of hydrogen gas is added, and the mixture is uniformly mixed; the reaction is carried out for 5 hours at the temperature of 80 ℃, the conversion rate of the 3-methoxy-2, 6-dichloro-4- (trifluoromethyl) pyridine is 86.1 percent, and the selectivity of the corresponding 3-methoxy-4-trifluoromethyl pyridine is 96.9 percent.
Example 68
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 3-carboxylic acid methyl ester-2, 6-dichloro-4- (trifluoromethyl) pyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), 0.5MPa of hydrogen gas was added, and the mixture was mixed uniformly; the reaction is carried out for 5 hours at the temperature of 80 ℃, the conversion rate of the 3-carboxylic acid methyl ester-2, 6-dichloro-4- (trifluoromethyl) pyridine is 72.5 percent, and the selectivity of the corresponding 3-carboxylic acid methyl ester-4-trifluoromethyl pyridine is 90.2 percent.
Example 69
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5.0%, the whole catalytic material mass percent in the mixture: 1.7%), 60mg of 3-cyano-2, 6-dichloro-4- (methoxy) pyridine (mass percent in the mixture: 1.0%), 60mg of diethylamine (mass percent in the mixture: 1.0%), 0.5MPa of hydrogen gas was added, and the mixture was mixed uniformly; the reaction is carried out for 5 hours at the temperature of 80 ℃, the conversion rate of the 3-cyano-2, 6-dichloro-4- (methoxyl) pyridine is 87.8 percent, and the selectivity of the corresponding 3-cyano-4-methoxyl pyridine is 97.3 percent.
Example 70
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass percent: 5%, mass percent of the whole catalytic material in the mixture: 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass percent in the mixture: 1.0%), 60mg of triethylamine (mass percent in the mixture: 1.0%), charging 0.5MPa of hydrogen, and mixing uniformly; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity for the corresponding 2-cyanopyridine of>99.0％。
Example 71
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass% is 5%, the mass% of the whole catalytic material in the mixture is 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture is 1.0%), 60mg of pyridine (mass% in the mixture is 1.0%), charging 0.5MPa of hydrogen, and mixing uniformly; the reaction is carried out for 5 hours at the temperature of 80 ℃, the conversion rate of the 2-chloro-6-cyanopyridine is 75.2 percent, and the selectivity of the corresponding 2-cyanopyridine is>99.0％。
Example 72
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass% is 5%, the mass% of the whole catalytic material in the mixture is 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture is 1.0%), 60mg of sodium carbonate (mass% in the mixture is 1.0%), hydrogen gas of 0.5MPa is added, and the mixture is uniformly mixed; the reaction is carried out for 5 hours at the temperature of 80 ℃, the conversion rate of the 2-chloro-6-cyanopyridine is 43.1 percent, and the selectivity of the corresponding 2-cyanopyridine is>99.0％。
Example 73
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass% is 5%, the mass% of the whole catalytic material in the mixture is 1.7%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture is 1.0%), 60mg of sodium bicarbonate (mass% in the mixture is 1.0%), hydrogen gas of 0.5MPa is added, and the mixture is uniformly mixed; the reaction is carried out for 5 hours at the temperature of 80 ℃, the conversion rate of the 2-chloro-6-cyanopyridine is 37.8 percent, and the selectivity of the corresponding 2-cyanopyridine is>99.0％。
Example 74
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass% is 5%, the mass% of the whole catalytic material in the mixture is 1.6%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture is 0.97%), 1mg of diethylamine (mass% in the mixture is 0.01%), hydrogen gas of 0.5MPa is added, and the mixture is uniformly mixed; the reaction is carried out for 5 hours at the temperature of 80 ℃, the conversion rate of the 2-chloro-6-cyanopyridine is 69.3 percent, and the selectivity of the corresponding 2-cyanopyridine is>99.0％。
Example 75
100mg of Pd/CeO was added to 6g of ethanol2(Pd loading mass% is 5%, the mass% of the whole catalytic material in the mixture is 1.3%), 60mg of 2-chloro-6-cyanopyridine (mass% in the mixture is 0.78%), 1.5g of diethylamine (mass% in the mixture is 19.6%), hydrogen gas of 0.5MPa is added, and the mixture is uniformly mixed; reaction at 80 deg.c for 5 hr, 2-chloro-6-cyanopyridine converting rate>99.0% with a selectivity for the corresponding 2-cyanopyridine of>99.0％。
Finally, it should be noted that the above-mentioned list is only a specific embodiment of the present invention. Obviously, the invention is not limited to the above embodiments, but may be modified in many ways, such as: Pd/CeO in the invention2Besides, different catalytic materials can also be applied to hydrogenation dehalogenation reaction of different heterocyclic halogen-containing organic matters, and the types of the loaded metal components, the loading amount, the reaction temperature and the reaction time can be varied. Can be directly derived or combined from the disclosure of the invention by a person of ordinary skill in the artAll such variations are considered to be within the scope of the invention.

Claims (4)

1. A method for catalyzing heterocyclic halogen-containing organic matters to be hydrodehalogenated by utilizing supported metal oxides is characterized by comprising the following steps:
(1) adding a solvent, heterocyclic halogen-containing organic matters, a neutralizer and a catalyst material into a sealable reaction vessel, and uniformly mixing; in the mixture, the mass percent of the catalyst material is 0.01-10%, the mass percent of the heterocyclic halogen-containing organic matter is 0.01-76.4%, the mass percent of the neutralizing agent is 0.01-19.6%, and the balance is solvent;
(2) filling hydrogen into the reaction container until the pressure is 0.1-3.0 MPa; controlling the reaction temperature to be 25-180 ℃ and the reaction time to be 0.1-24 hours; catalyzing and dehalogenating in the reaction process to finally obtain a dehalogenated heterocyclic compound;
in the catalyst material, the carrier is one or more of cerium oxide, titanium oxide, iron oxide, manganese oxide, cobalt oxide, aluminum oxide, silicon oxide, magnesium oxide and active carbon; the metal component loaded by the carrier is one or more of Au, Pd, Pt, Rh, Ir, Ni and Sn, and the mass percent of the metal component in the whole catalyst material is 0.1-30%.
2. The method according to claim 1, wherein the solvent is any one of: water, methanol, ethanol, tert-butanol, tert-amyl alcohol, toluene, dichloromethane, chloroform, dimethyl sulfoxide or acetone.
3. The method of claim 1, wherein the heterocyclic halogen-containing organic compound is any one or more of: 2-chloropyridine, 2-bromopyridine, 2-iodopyridine, 2-chlorothiophene, 2-chlorofuran, 2, 3-dichloropyridine, 2, 3-dibromopyridine, 2, 5-dichlorothiophene, 2-chloro-6-methoxypyridine, 2-chloro-6-trifluoromethylpyridine, 2-chloro-6-cyanopyridine, 5-chloro-3-thiophenecarbonitrile, 2-methyl-6-chloropyridine, 2-chloro-6-vinylpyridine, methyl 6-chloro-2-pyridinecarboxylate, 2, 6-dichloro-4- (trifluoromethyl) pyridine, 2, 6-dichloro-4-methoxypyridine, 2, 6-dichloro-4-cyanopyridine, 2, 3-dichlorothiophene, 2, 5-dichlorothiophene-carbonitrile, 2-chloro-6-methoxypyridine, 2-chloro-6-trifluoromethylpyridine, 2-chloro-, 3-cyano-2, 6-dichloro-4- (trifluoromethyl) pyridine, 3-methoxy-2, 6-dichloro-4- (trifluoromethyl) pyridine, 3-carboxylic acid methyl ester-2, 6-dichloro-4- (trifluoromethyl) pyridine, 3-cyano-2, 6-dichloro-4- (methoxy) pyridine.
4. The method of claim 1, wherein the neutralizing agent is any one of the following: pyridine, triethylamine, diethylamine, sodium bicarbonate or sodium carbonate.
CN201910531574.4A 2019-06-19 2019-06-19 Method for catalyzing heterocyclic halogen-containing organic matter hydrogenation dehalogenation by using supported metal oxide Pending CN111151248A (en)

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